CN109072269A - The method for producing biological product - Google Patents
The method for producing biological product Download PDFInfo
- Publication number
- CN109072269A CN109072269A CN201780025661.1A CN201780025661A CN109072269A CN 109072269 A CN109072269 A CN 109072269A CN 201780025661 A CN201780025661 A CN 201780025661A CN 109072269 A CN109072269 A CN 109072269A
- Authority
- CN
- China
- Prior art keywords
- lignocellulose biomass
- steam
- biomass
- pressurized reactor
- pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/02—Monosaccharides
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/04—Polysaccharides, i.e. compounds containing more than five saccharide radicals attached to each other by glycosidic bonds
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
- C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
- C12P7/10—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K1/00—Glucose; Glucose-containing syrups
- C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K13/00—Sugars not otherwise provided for in this class
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K13/00—Sugars not otherwise provided for in this class
- C13K13/002—Xylose
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C1/00—Pretreatment of the finely-divided materials before digesting
- D21C1/02—Pretreatment of the finely-divided materials before digesting with water or steam
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/0007—Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Zoology (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microbiology (AREA)
- Biotechnology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- Genetics & Genomics (AREA)
- Emergency Medicine (AREA)
- Processing Of Solid Wastes (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
A kind of method from lignocellulose biomass production biological product is disclosed, wherein lignocellulose biomass, gas and steam are introduced into pressurized reactor, which operates in a continuous manner under conditions of with steam head space.In pressurized reactor, steam head space is maintained at steam head space temperature and 1 bar of the pressure at least bigger than pure steam balance pressure at a temperature of steam head space.Then quick release pressure refines lignocellulose biomass to generate pretreated lignocellulose biomass while by the way that lignocellulosic is discharged from compressive reaction device assembly, is then hydrolyzed and is converted into biological product.Preferably, at least part gas be the air fallen into lignocellulose biomass and its be introduced into pressurized reactor as a part of lignocellulose biomass.In a preferred embodiment, before introducing pressurized reactor, soaking step and aerating step are carried out to lignocellulose biomass, and without any xylan separating step.
Description
Background
It is mono- using second generation technique glucose fermentation, the C6 as derived from the cellulose (glucan) of lignocellulose biomass
Biochemicals made from sugar and bio-fuel are opposite derived from the first generation technique of glucose of starch with fermentation.
It is well known that the C6 sugar in lignocellulose biomass is not easy to be contacted by enzyme and needs to pre-process to increase Portugal
Accessibility of the glycan to enzyme hydrolysis.In general, the pretreatment is related to steam blasting to open the cell of lignocellulose biomass simultaneously
So that glucan is easier to carry out subsequent enzyme hydrolysis and fermentation step.
It is also well known that lignocellulose biomass includes hemicellulose or xylan (C5 sugar) and hemicellulose
Xylan the steam blasting for lignocellulose biomass at a temperature of degrade.
WO2009/108773 is entitled " to utilize continuous prehydrolysis and steam blasting pretreating process preextraction hemicellulose
System and method " teach this Conventional wisdom and show that " high pressure and/or high temperature are being used to generate alcohol from cellulosic material, such as
Ethyl alcohol, pretreatment in be typical.In these conventional pretreatments, some C5 sugar are converted into inhibits hair after the pre-treatment
The component of the alcohol fermentation of C6 sugar in ferment step.Remove these constituents for suppressing, such as aldehyde (such as HMF, furfural and formaldehyde), monomer phenols
(such as vanillic aldehyde and coniferyl aldehyde), sour (such as formic acid) and other inhibitor should increase the production of the alcohol in C6 fermentation step after the pre-treatment
Amount."
It is not new that C5 sugar is separated from lignocellulose biomass.For example, nineteen fifty August 1st US2 announced, 516,
833 teach hydrolysis of lignocellulose biomass at low temperature is then handled at higher temperatures with recycling pentose (C5 sugar)
To recycle hexose (C6 sugar).Until today, this industry is continuing always this method.
The solution that WO2009/108773 is advocated utilizes well-known dual stage process, and wherein lignocellulosic is raw
Substance in a mild condition boiling to hydrolyze and dissolve the hemicellulose from charging.Charging flow into the second pressurized reactor with
In boiling charging before remaining cellulose, by hemicellulose dissolution in a liquid to extract C5 sugar.WO2009/108773 is pointed out
" after separating in the charging in tank, the C5 sugar in hemicellulose can be converted by conventional method as food additive
Add the xylose of agent, biogas is converted by aerobic and anaerobic fermentation, methylfuran and conversion are converted by Gaoxin alkoxide
It is aqueous sugar to be converted into alcohol, such as ethyl alcohol."
The dual stage process of the routine represents the current technology status of lignocellulose biomass manufacture field.
WO2010/113129 discloses the data for supporting that hemicellulose benefit is removed before steam blasting.Such as by giantreed (Arundo
Donax) steam blasting is carried out in the case where removing and without removing hemicellulose.When removing hemicellulose, in raw material only
1.3% xylan is degraded to inhibitor compound (embodiment 5) in pretreatment, and in the steam of no removal hemicellulose
In blasting process, the xylan degrading of 19.3% (embodiment 1) and 63.8% (embodiment 2) is inhibitor compound.
In fact, the inventor of Bertil Stromberg, WO2009/108773, support the understanding of industry, i.e., he in
2016 into the statement of U.S. Patent Office, while handle C5 and C6 sugar without generate apparent inhibitor be technically can not
Can.In the statement he point out " as in 512 patents [it is required that United States Patent (USP) of the priority of WO2009/108773] discuss,
Hemicellulose (predominantly 5 carbon sugar, in 512 patents also referred to as " C5 sugar ") is molten by hydrolysis in the first pressurized reactor
It solves and hydrolyzes.The C5 generated in the first pressurized reactor sugar is removed by wash feed and to charging draining.If no
Wash feed is simultaneously drained from charging, then C5 sugar can be retained in charging and degrade and be formed to subsequent in the second reactor
Enzyme hydrolysis and/or the potential inhibitor of fermentation step."
It should be evident that dual stage process needs at least two individual reactors, individually processing and recovery system, and
And and more consuming capital more more complicated in design than single reactor.
Therefore, it is necessary to a kind of preprocess method, high beta-dextran accessibility is provided and the recycling of high xylan is (i.e. a small amount of wooden poly-
Sugar degradation), without separating xylan from lignocellulose biomass, so as to avoid prior art motion and Conventional wisdom
66 years somewhat complex designs and schemes.
Summary
Disclose a kind of method by lignocellulose biomass production biological product, the lignocellulose biomass packet
Include the xylan of total amount, the glucan of total amount, total amount lignin and water.Method includes the following steps: by lignocellulosic
Biomass, the gas of total amount and steam are introduced into the pressurized reactor of compressive reaction device assembly, which is adding
Pressure reactor operates in a continuous manner under conditions of having steam head space, wherein a part of steam is in lignocellulose biomass
It is condensed on pressurized reactor；Keep the lignocellulosic that lignocellulose biomass is maintained at greater than 10 bars in pressurized reactor raw
Material pressure, residence time are 0.5 minute to 120 minutes, and steam head space temperature is within the scope of 130 DEG C to 230 DEG C, wherein wood
Matter cellulose biomass pressure ratio pure steam balance pressure at a temperature of steam head space is at least 1 bar big；By from pressurized reactor
Quick release lignocellulose biomass pressure is while lignocellulose biomass is discharged in component to generate pretreated wood
Matter cellulose biomass refines lignocellulose biomass；At least part glucan is hydrolyzed into a certain amount of glucose；
Biological product is converted by the glucose of at least part amount.
Also disclosing lignocellulose biomass may further include the air fallen into, and at least part gas can
The air of pressurized reactor fallen into is introduced to be as lignocellulose biomass a part.
Further disclosing this method may further include xylan separating step, wherein introduce pressurized reactor
Before, the xylan less than total amount 15% is separated from lignocellulose biomass.
Also disclose the separating step that this method can not include xylan before introducing pressurized reactor.
Further disclosing this method may further include soaking step, wherein draw by lignocellulose biomass
Before entering pressurized reactor, lignocellulose biomass is immersed in the liquid including water.
Also disclosing this method may further include aerating step, wherein by by wooden fibre after soaking step
Dimension cellulosic biomass is exposed to air and is aerated lignocellulose biomass.
Further disclose, by lignocellulose biomass introduce pressurized reactor before, can at 25 DEG C to less than
Lignocellulose biomass is compressed within the scope of 100 DEG C of compression temperature.
Pressurized reactor is also disclosed with pressurized reactor volume, and steam head space has steam head space volume,
It can be between the 5% to 80% of pressurized reactor volume.
It further discloses and can choose lignocellulose biomass pressure so that refining step is to lignocellulosic biomass
Matter carries out steam blasting.
It also discloses and can control steam head space temperature and residence time to recycle pretreated lignocellulosic biomass
It is more than the xylan of total amount 65% in matter.
It further discloses and can control lignocellulose biomass pressure, so that pretreated lignocellulose biomass
Including a certain amount of accessible glucan, and the amount for the glucan that can contact in pretreated lignocellulose biomass is opposite
The total amount of glucan is greater than 80% in pretreated lignocellulose biomass.
It is described in detail
Method of the invention depends on following discovery: before gas being added steam phase and carrying out steam blasting, C5 sugar (wood
Glycan) it need not be removed from lignocellulose biomass.As being confirmed test portion, gas addition steam phase is increased
For the gross pressure of steam blasting lignocellulosic cellulosic biomass, and at the same time being reduced to balance to steam temperature under the partial pressure of steam
Stripping temperature.In this way, steam blasting carries out (forming considerably less inhibitor) at a temperature of minimum C5 sugar is degraded
And steam blasting be also performed such that at high enough pressure C6 sugared (glucan) to enzyme can and.In this way, it eliminates
The first pressurized reactor in the two stages system, and significantly reduce steam consumption.
It has also been found that by eliminating the first boiling step in the prior art, be capable of providing sufficient amount and lignocellulosic
Biomass enters the air (gas) of steam blasting process together to carry out the process.This is astonishing, because from paper/paper
Matter textbook removes air before being heat-treated lignocellulose biomass to almost generally teaching in the prior art for patent.
For example, the US4 according to Reitter in 1984,427,453, one is use the continuous pipe type boiling with worm screw feeder
Device, because " not no excess liq substantially can be injected to the reaction under high pressure space of boiling vessel by using worm screw feeder, more
Importantly, the not no chip material of air inclusion substantially, this is unfavorable to hydrolysis " and " it is emphasized that technique
Key point be the air that almost 100% can be removed by using worm screw press machine, this be to hydrolysis it is extremely harmful, from cutting
Broken biomass enters before boiling vessel."
Introduction and Conventional wisdom with the prior art on the contrary, the inventors discovered that by not eliminating the air in biomass,
The temperature of reactor can will be reduced in enough air induction systems and kept while being handled needed for xylan and glucan
High pressure, it is sugared (xylan) to recycle a large amount of C5, and steam blasting lignocellulosic cellulosic biomass is in subsequent enzyme hydrolysis
C6 sugared (glucan) accessibility high to enzyme is provided during step.
Method of the invention is the method from lignocellulose biomass production biological product.This method connects at least one
The pressurized reactor of reforwarding row.By continuous operation, either optionally continuously runs or operate mean wood in a continuous manner
Matter cellulose biomass can remove it while entering pressurized reactor from reactor.
Lignocellulose biomass will be made of xylan, glucan, lignin, water and optional air.Wood fibre
The xylan, glucan and lignin that cellulosic biomass will have the total amount in terms of butt.The water that it will also have weight percent,
It is expressed as the percentage of the lignocellulose biomass total weight comprising water.Lignocellulose biomass will usually have or attached
Thereon or intracellular air soluble in water and/or lignocellulosic structure.Lignocellulose biomass can be
A part of lignocellulose biomass feeding flow.
Xylan is the polysaccharide made of xylose (pentose) unit.Xylan is also known as a part of the carbohydrate of C5.
Xylan includes the β-D- xylose units mainly connected.The total amount of xylan is the xylose equivalent in lignocellulose biomass
Weight.
Glucan is the polysaccharide of D-Glucose (hexose) monomer.Glucan is a part of C6 carbohydrate.The total amount of glucan
It is the weight of the glucose equivalent in lignocellulose biomass.
Lignin, which is typically considered, is made the wooden alcohol monomer of the list of tonquinol, coniferyl alcohol and sinapinic alcohol of different amounts of
Polymer.When being present in lignocellulose biomass, which refers to that term lignin total amount refers to that lignocellulosic is raw
The weight of the polymer of three kinds of wooden alcohol monomers in substance, the oligomer of three kinds of wooden alcohol monomers and monomer itself, if they
In the presence of if.
The detailed description of lignocellulosic feedstock can in WO2015028156A1 11-14 pages find, by reference to
Mode is incorporated herein.Preferred lignocellulosic feedstock be selected from the group of agricultural residue, especially switchgrass, Chinese silvergrass, giantreed and
Bagasse, such as sugarcane, bagasse and stalk such as straw, straw, hardwood and cork also benefit from this method.
In the method, the lignocellulosic biomass that will be made of the xylan of total amount, the glucan of total amount and lignin
Matter and steam and gas are concomitantly introduced into the pressurized reactor in compressive reaction device assembly.The pressurized reactor is transported in a continuous manner
Turn.
Steam can be term known in the art " liquid water-steam mixture ", " saturated vapor " or " overheat is steamed
A part of vapour ".
Although lignocellulose biomass can enter pressurized reactor at any temperature, entering pressurized reactor
Before, preferred range is the temperature within the scope of 25 DEG C to 140 DEG C.Since pressurized reactor operates under reactor pressure, wood
It is anti-that matter cellulose biomass usually enters pressurization under big or preferably bigger pressure at least as pressurized reactor pressure
Answer device.Compression is usually applied on lignocellulose biomass by compression set (such as plug screw-feeder) water is discharged
And increase pressure into pressurized reactor.It is preferred that lignocellulose biomass to be introduced to pressure in the case where compression temperature is less than 100 DEG C
Compression apparatus, and compression temperature is preferably in the range of 25 DEG C to less than 100 DEG C, more preferable compression temperature at 25 DEG C to 95 DEG C,
Most preferably compression temperature is at 30 DEG C to 90 DEG C.
Pressurized reactor, which can be horizontal reactor, vertical reactor or stick up oblique or crooked reactor, (also referred to as to incline
Oblique reactor), lignocellulose biomass flows (relative to gravity upwardly or downwardly or vertically) in any direction.
Pressurized reactor, which has in pressurized reactor under conditions of steam head space, to be operated.This means that reactor is not with it
100% volume is operated full of lignocellulose biomass.The steam head space of pressurized reactor is term well known in the art,
Refer to a part of the reactor in reactor above liquid and/or solid (lignocellulose biomass).In addition to can be with
It (is such as risen in reactor on lignocellulose biomass level simultaneously on the wall of reactor or on internal some parts
In the blender axis or screw conveyor in steam head space) condensation liquid (such as water) except, the steam of pressurized reactor
Liquid or solid in head space is seldom.
Steam head space has a volume, referred to as steam head space volume, is expressed as the percentage of pressurized reactor volume.
The volume of pressurized reactor is known as pressurized reactor volume.Usual steam head space volume pressurized reactor volume 5% to
In the range of 80%, more preferably between the 10% to 80% of pressurized reactor volume, more preferably in compressive reaction body
Between long-pending 15% to 75%, and more preferably between the 25% to 75% of pressurized reactor volume, most preferably, adding
Between press reactor volume 35% to 65%.
It is not the gas of steam that gas used in this method, which is under the conditions of the temperature and pressure of pressurized reactor,.Steam
Exist as steam.Since steam is steam rather than gas, i.e., steam is deposited with the balance of liquid water present in pressurized reactor
?.The gas being introduced into does not have the steam balanced with respective liquid in reactor.Therefore, gas will not be in the temperature of steam head space
With condensed under pressure.Such representative gases include but is not limited to that nitrogen, oxygen, carbon dioxide and many volatility are organic
Compound.Term gas also includes the mixture containing gas, and the gas does not form the liquid phase with gas balance, such as empty
Gas.
Pressurized reactor is a part of reactor assemblies.Reactor assemblies are generally included for by lignocellulosic biomass
Matter is loaded into the feeding device in pressurized reactor.Feeding device can also be continuously or with equal fractions or pulsed operating, should
Process is continuous process because lignocellulose biomass lignocellulose biomass while entering pressurized reactor is moved
Reactor out.Compression screw rod and rotation air lock valve are the examples of feeding device well known in the art.Reactor assemblies also have use
In the discharger that lignocellulose biomass is discharged or removed from reactor.Select discharger wooden with quick release
Cellulose biomass pressure simultaneously refines lignocellulose biomass.Refining lignocellulose biomass means to reduce ruler
It is very little.It carries out refining the cell rupture that can make lignocellulose biomass, i.e. steam blasting by quickly reducing pressure.Refine step
Rapid steam blasting lignocellulose biomass it is also known that.These methods are in the resistance to special fiberboard of Mason the 1930s
(Masonite) it is used in the invention of rifle.
When steam enters pressurized reactor, at least part steam is condensed into liquid on lignocellulose biomass
Water.In this way, the latent heat of vaporization improves the temperature of lignocellulose biomass from steam-transfer to lignocellulose biomass
Degree.Steam is condensate in the vapour-liquid equilibrium that difference steam and gas is established in biomass.Steam as with its liquid water shape
The steam of formula balance exists.Gas does not have liquid form under reactor condition.
Therefore, it can be said that the first step of this method is to introduce lignocellulose biomass, the gas of total amount and steam to add
In the pressurized reactor for pressing reactor assemblies, under conditions of which has steam head space in pressurized reactor
Operating, a portion steam are condensate on lignocellulose biomass.
The point that each element introduces may not necessarily be same point.Steam can be simultaneously from reactor head, reactor bottom
Portion, reactor side or all positions enter.Gas can enter reactor in the same manner.
Preferably, when gas enters as air, as the air fallen into, as lignocellulose biomass one
Part enters.The air fallen into is the intracellular air of lignocellulose biomass, is dissolved in lignocellulose biomass water
Or adheres to or be adhered on lignocellulose biomass.
The next step of this method will be in pressurized reactor at a temperature of being the steam head space within the scope of 130 DEG C to 230 DEG C
Lignocellulose biomass keeps or maintains 0.5 minute to 120 minutes residence time.Preferably, the residence time was at 1 minute
Within the scope of 60 minutes, it is highly preferred that from 1 minute to 30 minute, and most preferably, from 1 minute to 15 minute.Steam head space temperature
Degree is preferably within the scope of 150 DEG C to 220 DEG C, more preferably at 160 DEG C to 210 DEG C, and most preferably at 170 to 200 DEG C.
Term " residence time " refers to that lignocellulose biomass enters reactor and lignocellulose biomass leaves
Elapsed time between (being discharged from).The selection of residence time has very big range.Lower temperature will allow longer stop
The time is stayed to obtain optimum point of production, and higher temperature needs the shorter residence time to avoid the degradation of xylan.
It is controlled under given steam headspace pressure by changing the gas flow relative to quantity of steam in steam head space
Steam head space temperature.The case where air is introduced into as lignocellulose biomass or lignocellulosic feedstock stream a part
Under, the air capacity relative to quantity of steam in steam head space can be changed by changing the volume of steam head space, that is, compressive reaction
The fill factor of device.Therefore, the fill factor of pressurized reactor can be used as control parameter to a certain extent.With reference to being steam
Head space temperature, major part are identical as the steam temperature being condensate on lignocellulose biomass.In this way, it vaporizes
Heat discharges on lignocellulose biomass particle surface.Due to the heat-transfer character of lignocellulose biomass, lignocellulosic
Biomass will improve temperature when passing through pressurized reactor.When entering pressurized reactor from it with lignocellulose biomass
Lignocellulose biomass enters temperature heating and close to the temperature of condensed steam, and computer mould, which fits plant experimental, to be used to
Determine heating rate.
Enter the position of pressurized reactor depending on steam, steam is condensate on lignocellulose biomass at the time of contact.
If steam is condensate at the top of the lignocellulose biomass of steam head space, water will flow downwardly into lignocellulose biomass
In.If steam is condensate in the bottom of pressurized reactor, some steam are condensed and rest part is because be moved upwards up to steam
Head space and continue through lignocellulose biomass.Pass through reactor, lignocellulosic as lignocellulose biomass is mobile
Biomass temperature during the residence time rises.Therefore, lignocellulose biomass may never reach steam head space temperature
Degree.
The meaning of temperature curve is that traditional seriousness processing parameter is only that the single order being heat-treated in continuous process is estimated
Meter.
Steam head space has steam headspace pressure.Steam head space will operate under the steam headspace pressure, the steam head space
Pressure is that pure steam at a temperature of steam head space balances pressure plus the partial pressure at a temperature of steam head space.Fixed steam top
Steam head space temperature will decline as the steam static headspace gas scale of construction increases when pneumatics power.By the way that gas is added to pressurized reactor
In, temperature and pressure is separated from pure steam equilibrium condition.
This has obtained best description in the following table, and the table shows gas flows in fixed steam headspace pressure or 23 bars
Lignocellulose biomass pressure under how to influence temperature, reference gas is air.
Influence of 1. gas of table to steam head space temperature
It can easily be seen that the rest part of steam head space is steam by the way that gas is maintained at 84.3 moles of % of steam head space
(i.e. steam), 23 bars of steam head space temperature can control at 140 DEG C.
Steam headspace pressure is greater than pure steam at a temperature of steam head space and balances pressure, is equal to lignocellulose biomass
Pressure, because the static pressure that lignocellulose biomass passes through its height of bed can be ignored and be neglected for the purpose of this method
Slightly.Because pressure and temperature is not balanced further according to pure steam and coupled, steam headspace pressure (is equal to lignocellulose biomass pressure
Power) it is at least 0.5 bar bigger than pure steam balance pressure at a temperature of steam head space.Although 0.5 bar is minimum difference, more preferably
Be it is 1 bar big, it is more preferably 1.5 bars big, it is preferred 2 bars big, most preferably greatly to 6 bars.
Steam headspace pressure (and lignocellulose biomass pressure) in pressurized reactor should be at least 10 bars with
Just best promote refining step and preferably steam blasting lignocellulosic cellulosic biomass, preferably at least 13 bars, it is even more excellent
It is selected as at least 15 bars, and most preferably 18 bars.When the lignocellulose biomass of steam blasting enters saccharification/enzyme hydrolysis stage
When, steam blasting makes glucan be easier to be contacted by enzyme.Even if the advantages of disclosed method first is that in very high steam head space
It is operated under pressure (i.e. non-degradable sugar), preferred steam headspace pressure (and lignocellulose biomass pressure) is because of actual cause
(such as the excessively high cost for avoiding pressurized reactor) is less than 30 bars.Therefore, steam headspace pressure (and lignocellulose biomass
Pressure) can in the range of 10 to 30 bars perhaps 13 to 30 bars perhaps 15 to 30 bars or 18 to 30 bars.
For example, controlling the residence time by the rotation speed of the screw conveyor in control horizontal reactor.It can also be with
The residence time is controlled by controlling the amount of the lignocellulose biomass entered in pressurized reactor.
Those of ordinary skill will recognize by controlling the rate of biomass across reactor, quantity of steam, gas flow, life
The particle size of the stirring of substance or Surface Renewal and biomass, can be in given steam head space temperature and steam head space
Reach the optimal pretreatment residence time under pressure (i.e. lignocellulose biomass pressure).
Those of ordinary skill can control steam head space temperature and residence time as previously described, so that leaving reactor assemblies
Pretreated lignocellulose biomass in be greater than total amount 65% xylan can be recovered.Recycling refers in terms of butt
The amount of xylan equivalent in the lignocellulose biomass of Measurement preprocessing, and (this feelings are expressed as before reference point
It is before entering pressurized reactor under condition) percentage of xylan equivalent total amount in lignocellulose biomass.It is testing
Part lists the amount of xylan in measurement lignocellulose biomass to calculate the process of xylan recycling.For example, if grinding
It grinds lignocellulose biomass and measures lignocellulosic biomass per ton in terms of butt immediately before entering pressurized reactor
200 kilograms of total pentosans (being expressed as xylan equivalent) in matter, 65% xylan recycling mean pretreated wood per ton
There is 130 kilograms of xylans (being expressed as xylan equivalent) in matter cellulose biomass.It can although the xylan of 65% recycling is
The amount of realization, but the data of experimental section show that this method can be realized at least 70% recycling xylan, more preferably at least
The xylan of 75% recycling, the xylan of most preferably at least 80% recycling.
If the 80% of xylan primary quantity is recovered, the maximum value for the xylan degraded is 20%.
Therefore, the second step of this method can be described as the lignocellulose biomass in pressurized reactor in wooden fibre
It ties up under cellulosic biomass pressure, steam head space temperature is kept for 0.5 minute to 120 minutes within the scope of 130 DEG C to 230 DEG C；Wherein, it controls
Steam head space temperature processed and residence time are to recycle the xylan for being greater than total amount 65% in pretreated lignocellulose biomass.
The third step of this method is to refine lignocellulose biomass.Refining lignocellulose biomass means to reduce wood
The size of matter cellulose grain.In the method, by the way that the same of lignocellulose biomass is discharged from compressive reaction device assembly
When quick release lignocellulose biomass pressure come complete refine to generate pretreated lignocellulose biomass.Work as pressure
When declining sufficiently high, lignocellulose biomass is by explosion.That is, pressure decline is sufficiently fast and big so that lignocellulosic
The cell experience of biomass is known as the process of steam blasting.As shown in the experimental section, in the method, may be implemented in enzyme water
Glucan is solved in step to high pressure required by the good accessibility of enzyme, without to height relevant with those high pressures in history
Vapor (steam) temperature is associated.In this way, C5 sugared (xylan) is non-degradable, but that recycles can be connect with C6 sugared (glucan)
Closely.This steam blasting uses the discharger designed for steam blasting.Because steam explosion technology has existed many decades, steam
Steam explosion is broken discharger and is well known in the art.
Therefore, while third step can be described as by the way that lignocellulose biomass is discharged from compressive reaction device assembly
Quick release lignocellulose biomass pressure refines lignocellulose biomass, raw to generate pretreated lignocellulosic
Substance.
After reading specification, those of ordinary skill is it should be understood that pretreated lignocellulose biomass includes certain
Measure come-at-able glucan, and in pretreated lignocellulose biomass come-at-able glucan amount relative to pretreatment
Lignocellulose biomass in glucan total amount be greater than 80%.
The amount of come-at-able glucan in pretreated lignocellulose biomass is defined as can be used for enzyme hydrolysis and can
Be converted into glucose for fermentation glucan amount.Come-at-able glucan is measured as what experimental section defined.Pre- place
Glucan total amount in the lignocellulose biomass of reason is self-evident and is determined according to the method that experimental section defines
's.
Since the amount of the mainly pressure of release has determined xylan accessibility, those of ordinary skill controls lignocellulosic
Biomass pressure (i.e. steam headspace pressure) makes pretreated lignocellulose biomass include that a certain amount of come-at-able Portugal is poly-
Sugar, and the amount of come-at-able glucan is given birth to relative to pretreated lignocellulosic in pretreated lignocellulose biomass
The total amount of glucan is greater than 80% in substance.Lignocellulose biomass pressure is identical as steam headspace pressure, is on steam top
Balance of steam pressure at empty temperature at a temperature of steam head space in steam head space partial pressure summation.As previously shown, it steams
Vapour headspace pressure is determined by the quantity of steam in the gas flow and steam head space in steam head space.
It has also been found that lignocellulose biomass can be used as including air (to avoid thinking necessary air in history
Removal process) lignocellulose biomass feeding flow introduce, and a part as lignocellulose biomass feeding flow
The percentage of the gas of introducing is 50%, 70% and the 90% of the gas gross that at least choosing is freely introduced into pressurized reactor, very
To the value of the group of 100% composition.
Even it is possible that all gas as shown in experimental section (such as air), as lignocellulose biomass
Or a part of lignocellulosic feedstock stream introduces.In other words, all gas is all derived from original position, and gas is not
It is respectively added to feeding flow or pressurized reactor.It is believed that be introduced into the air that falls into lignocellulose biomass relative to from
For isolated entrance addition air or gas, it can further improve the refining step of lignocellulose biomass, because
The presence of air can cause more effective cell explosion.
Another embodiment of this method further includes will be wooden before lignocellulose biomass is introduced pressurized reactor
Matter cellulose biomass is immersed in the liquid including water.Soaking step is well known in the art and can be many different
Soaking temperature and pressure under complete.Lignocellulose biomass can be dehydrated before introducing pressurized reactor.Preferably, it soaks
Bubble can less than 100 DEG C temperature and atmospheric pressure under complete to avoid using expensive pressurized equipment or vacuum.
Under the soaking temperature lower than 100 DEG C, hemicellulose (xylan) will not dissolve a lot and most of (if not
It is all) it can enter in pressurized reactor together with lignocellulose biomass.In addition, in atmospheric pressure and temperature lower than 100 DEG C
Lower impregnate of degree remains unchanged the air being entrained in lignocellulose biomass, allows air and lignocellulosic biomass
Matter enters pressurized reactor together.
Preferred soaking cycle is carried out in the case where lignocellulose biomass and air contact.This can pass through
Lignocellulose biomass is introduced into water-filled fermentation vat or container and is realized, wherein the Free Surface of water is exposed to greatly
Gas.Lignocellulose biomass (usual density is less than water) will swim on the water surface and can periodically soak mechanically
Not yet, to keep the air and xylan in lignocellulose biomass while soaking lignocellulose biomass.If there is
Selectable soaking step then preferably remains operating condition and makes the xylan less than 15% weight in lignocellulose biomass
It is separated before being introduced into pressurized reactor with lignocellulose biomass, preferably smaller than the xylan of 10% weight is in wood fibre
Cellulosic biomass separates before being introduced into pressurized reactor with lignocellulose biomass, and the wood of more preferably less than 5% weight
Glycan separates before lignocellulose biomass is introduced into pressurized reactor with lignocellulose biomass, most preferably without wood
Glycan separates before lignocellulose biomass is introduced into pressurized reactor with lignocellulose biomass.
Although xylan separating step be it is selectable, lignocellulose biomass is preferably being introduced into pressurized reactor
Xylan is not separated from lignocellulose biomass before, so as to eliminate equipment associated with the separating step cost and
Complexity.If there is selectable xylan separating step before lignocellulose biomass is introduced into pressurized reactor,
Preferably remain xylan separating step operating condition make before lignocellulose biomass is introduced into pressurized reactor from
Removal is less than the xylan of 15% weight in lignocellulose biomass, and it is anti-to be preferably introduced into pressurization in lignocellulose biomass
The xylan for removing from lignocellulose biomass before device and being less than 10% weight is answered, and more preferably raw in lignocellulosic
Substance is introduced into the xylan for removing from lignocellulose biomass before pressurized reactor and being less than 5% weight, most preferably exists
Lignocellulose biomass does not have xylan to remove from lignocellulose biomass before being introduced into pressurized reactor.
It has also been found that, lignocellulose biomass can be used as including lignocellulose biomass and sky in one embodiment
The lignocellulose biomass feeding flow of gas is introduced into pressurized reactor, and wherein air is gas.The air can be entrained in life
It in substance and is not removed before entering pressurized reactor or the air can come from the exposure to biomass after dipping
Gas.An exemplary embodiment of the aerating step is described in experimental section, but simplest form is by biomass exposure
In air or atmosphere.Aeration time was preferably for 10 seconds, more preferably greater than 30 seconds, most preferably greater than 60 seconds.Although not exposing
The gas upper limit, but preferably aeration time was less than 1 hour.Finally, aerating step may include that the biomass of immersion is exposed to pressure
Air stream.
In a preferred embodiment, the lignocellulose biomass of immersion carries out before being introduced into pressurized reactor
Dehydration.Dehydration may include drain step under the effect of gravity to remove at least part free water or liquid, with
And compression step is to remove at least part immersion liquid in lignocellulose biomass.Aerating step preferably compression step it
It is all or part of afterwards to carry out, and may include softening lignocellulose biomass, this becomes lignocellulose biomass
Pine is to reduce bulk density relative to bulk density at the end of compression step.The lignocellulose biomass of compression it is soft
Change can be obtained by mechanical action method, such as distribution screw rod.Although air is preferred gas, this method can also include
It will not be that the additional gas of air is introduced into pressurized reactor.In fact, in one embodiment, air is raw in lignocellulosic
Atmosphere in at least one of substance or water, and the lignocellulose biomass and water before being introduced into pressurized reactor not
Step is removed by air.
There are many methods that lignocellulose biomass is transported by reactor, and a kind of method is by lignocellulosic
Biomass is mechanically transported from the entrance of pressurized reactor to the outlet of pressurized reactor.Producing pretreated lignocellulosic
After biological mass flow, lignocellulose biomass is exposed at least one hydrolyst such as enzyme or metal, will at least one
Portion of dextran is hydrolyzed to glucose.The hydrolysing step is well known in the art, and it refers to enzyme water when using enzymes
Solution.
After at least part glucan is hydrolyzed to glucose, at least part glucose is converted into biological product.Most
Common biological product is the bio-ethanol produced and glucose is placed in the presence of yeast.Convert glucose into biology
This technology (such as bio-ethanol) of product is well known.Such as manufactured grape wine and converting glucose into ethyl alcohol
And beer.Usually for industrial purpose, with the consumption purpose of beer and grape wine on the contrary, bio-ethanol is distilled and purifies.
Hydrolysis and fermentation process detailed description, for example, be contained in Charles E.Wyman, Taylor in 1996 and
The bio-ethanol handbook of Francis: in production and use.
Test
Lignocellulose biomass used in report experiment is the materials of wheat stalk with 90% weight dry matter.
Using three kinds of different experimental groups come the advantages of confirming disclosed method.
First experimental group (control)
First experimental group makes lignocellulose biomass undergo the continuous preprocessing process of two steps, and wherein xylan is first
In pressurized reactor it is mild under the conditions of dissolve in the first pre-treatment step for carrying out, the then harsh item in the second pressurized reactor
It will gather including water and the wood of dissolution before carrying out the second pre-treatment step to the lignocellulose biomass that xylan exhausts under part
The liquid of sugar is separated from lignocellulose biomass, and carries out steam blasting step.According to the general religion of WO2009/108773
Lead, the first experimental group operates whole process under an increased pressure, thus prevent lignocellulose biomass in whole process and
It is contacted before the second pre-treatment step especially in the second pressurized reactor with atmosphere.
First pressurized reactor is vertical reactor.It is raw that lignocellulosic is continually introduced at the top of the first pressurized reactor
Substance and by introduce steam carry out pre-treatment step.First pressurized reactor is pressurizeed by steam.Lignocellulosic biomass
Matter introduces the first pressurized reactor by pre- steam engine, and pre- steam engine is standard device used in wood pulp system and program, with
With steam pre-treatment lignocellulose biomass and remove the air fallen into.Therefore, in the first pressurized reactor, if deposited
The amount of air is very limited.First pre-treatment step is in the xylan for being enough dissolving lignocellulose biomass and has
(being shown in Table 2) carries out under the conditions of limiting the mild temperature of xylan degrading.By lignocellulose biomass from the first pressurized reactor
Bottom is removed in the form of the slurries of dry matter 5%, then flows into the second pressurized reactor under an increased pressure.In first and
Between two pressurized reactors, by inclination water trap under gravity draining by free fluid from lignocellulose biomass
It removes in slurries, is substantially being operated under the steam pressurized conditions of identical pressure and temperature in the first pressurized reactor.It is free
Liquid is separated from lignocellulose biomass, and the xylan including water and dissolution is collected into tank.By plug spiral into
By the second pressurized reactor of lignocellulose biomass insert continually that drain, xylan exhausts, (it is Horizontal cylinder to glassware
Shaped reaction device) in, it is subjected to lignocellulose biomass shear with compressing force to be formed continuously lignocellulose biomass plug,
The pressure difference being able to maintain between pressurized reactor and plug screw-feeder entrance, the plug screw-feeder entrance are generally in
The steam pressure of first pressurized reactor.The temperature of the lignocellulose biomass of plug screw-feeder inlet adds with first
The temperature of pressure reactor is roughly the same and dry matter content is about 15%.
A part of immersion liquid in lignocellulose biomass, the xylan including water and dissolution, passes through plug spiral
Feeder is removed and is collected.Immersion liquid is included in the liquid in lignocellulose biomass, although being eliminated by gravity
Free fluid, but immersion liquid needs certain mechanical action to remove.In the second pressurized reactor, xylan exhausts wooden
Cellulose biomass is entered with about 45% dry matter, and one group of steam inlet by being distributed in the second pressurized reactor side
The steam of saturation is inserted into be pre-processed.Steam stream passes through the lignocellulose biomass stream with entrance reactor in terms of butt
The proportion adjustment of weight 1:1 per hour.It is in the steam pressure into before reactor of the back side measurement of a steam inlet
21 bars, and corresponding vapor (steam) temperature is 216 DEG C.In the second pressurized reactor, lignocellulose biomass is subjected to than
The more harsh temperature condition for the more short residence time that (is shown in Table 2) in one pressurized reactor.It will be wooden by the screw rod of inside reactor
Matter cellulose biomass is transported from the entrance of horizontal second pressurized reactor to outlet, and is controlled by the revolving speed of change screw rod
Residence time processed.Second pressurized reactor is operated with about 30% fill factor, and constantly measures the steam top of reactor
Empty temperature and pressure.After the second pre-treatment step in the second pressurized reactor, lignocellulose biomass passes through connection
To reactor outlet gas blow pipe steam blasting and recycled in the air blowing cyclone separator under about 0.5 bar pressure.
Second experimental group
In the second experimental group, the pretreatment system of the first experimental group is operated so that lignocellulose biomass is small in temperature
Soaking step is carried out in 100 DEG C of water and contacts atmosphere, to increase the water content of lignocellulose biomass and remove wooden
Some non-wooden cellulose's components of cellulose biomass.Non-wooden cellulose's component of lignocellulose biomass includes extracting
Object such as salt, wax and protein and from harvest step external contaminants such as dust, stone and metal fragment.Due to low immersion
Temperature does not extract xylan in soaking step.Then, in the lignocellulose biomass that will be impregnated in compressive reaction
Critical conditions under carry out unique pre-treatment step before, the liquid of non-wooden cellulose's component that will include water and be removed
It is separated from lignocellulose biomass, and carries out steam blasting step.Second experimental group includes a pressurized reactor, and
Lignocellulose biomass is allowed access into before introducing pressurized reactor contacts with air, and pressurized reactor is the first experimental group
The second pressurized reactor.
Lignocellulose biomass is inserted into the first vertical reactor of the first experimental group, which is non-steam
It is operated under pressurized conditions.In the first vertical reactor thus as soaking container operation, make wooden fibre by being inserted into steam
Dimension cellulosic biomass carries out the soaking step of 40 minutes soaking times under less than 100 DEG C of temperature and 1 bar.Soaking container is about
It is operated under 30% fill factor, and not to external atmospheric sealing, therefore air is present in the top of soaking container.Cause
This, during soaking step, the lignocellulose biomass in soaking container is by limited air exposure.By lignocellulosic
Biomass is removed with the slurry form of dry matter 5% from the bottom of soaking container, then flows to the second experimental group under atmospheric pressure
Unique pressurized reactor.Between soaking container and pressurized reactor, by being drained under gravity in inclination water trap,
Free immersion liquid is extracted from lignocellulose biomass slurries, inclination water trap lies also in the lower operation of atmosphere contact.From this
It is withdrawn in method free immersion liquid (extract including water, external contaminants and lignocellulose biomass).The liquid of removal
Xylan is not detected in body.The solid lignocellulosic biomass matter of discharge pass through together with the air fallen into plug spiral into
Glassware is inserted into pressurized reactor, is removed the liquid of a part immersion by plug screw-feeder and is withdrawn during this.
Lignocellulosic temperature in plug screw-feeder inlet is 80 DEG C and dry matter is about 15%.Immersion liquid includes
Water, the extract of external contaminants and lignocellulose biomass and no xylan.Lignocellulose biomass is with about
45% dry matter enters pressurized reactor.
The portion of air in lignocellulose biomass is fallen into, but is not all of, it can be together with a part of immersion liquid
It is removed by plug screw-feeder.That is, the lignocellulosic biomass in preliminary test, close to the outlet of plug screw-feeder
The density of matter plug is close significantly less than the high densification sample that the lignocellulose biomass impregnated by compression individually produces
Degree.
In pressurized reactor, pre-processed by being used in the identical program being described in detail in the first experimental group insertion saturated vapor
The lignocellulose biomass of immersion.After pre-treatment step in pressurized reactor, lignocellulose biomass is by blowing
Tracheae steam blasting and in air blowing cyclone separator to be recycled under about 0.5 bar of pressure.
In the second experimental group, the solid lignocellulosic biomass matter of discharge is also exposed to air in inclination water trap,
And until being introduced into plug screw-feeder.But, it is exposed to air to be limited in a certain degree, because of lignocellulosic biomass
Matter is compacted due to the influence of gravity in soaking container and inclination water trap.
Whole process continuous operation.
Third experimental group
Third experimental group include in the second experimental group soaking container (i.e. under atmospheric pressure with air touch operation first
First vertical reactor of experimental group), operate for the lignocellulose biomass of immersion to be dehydrated and is aerated under atmosphere
System and the horizontal pressure reactor described in previous experimental group.About the second experimental group, third experimental group is designed to
After soaking step and before lignocellulose biomass is introduced pressurized reactor, increase lignocellulose biomass to sky
The exposure of gas, therefore increase the air capacity for introducing pressurized reactor together with lignocellulose biomass.
Firstly, lignocellulose biomass undergoes soaking step described in the second experimental group.Lignocellulosic is raw
Substance is inserted into before pressurized reactor, removes free fluid and a part of immersion liquid in succession in multistep dehydration.De-
During water, it is aerated lignocellulose biomass by being exposed to atmosphere, to increase the air capacity fallen into biomass.Firstly,
It is drained under the effect of gravity by the horizontal surface (band) of perforation to remove free fluid.During the step, in addition to gravity it
It is outer to be applied on lignocellulose biomass without mechanical action to avoid the stomata of closure lignocellulose biomass.By wearing
The first horizontal distribution screw rod distribution lignocellulose biomass on the horizontal surface in hole is to be discharged free fluid.Operate horizontal point
With screw rod with the height of balanced lignocellulose biomass without applying significant compression, to increase the wooden fibre for being exposed to air
It ties up the surface of cellulosic biomass and falls into the air capacity in biomass.Then a part of immersion liquid in belt filter press by pressing
Contracting is removed from lignocellulose biomass.After compression step, lignocellulose biomass is assigned to horizontal surface and is led to
Crossing the second horizontal distribution screw rod makes lignocellulose biomass fluff, to carry out the second aerating step to it.Carry out dehydration and
The time of aeration is variation, and the shortest time is 1 minute.By plug screw-feeder by lignocellulose biomass together with sunken
Air in blowhole is together in insert continually horizontal pressure reactor.Lignocellulosic in plug screw-feeder inlet
Biomass temperature is 70 DEG C and dry matter is 22%.In plug screw-feeder, another part immersion liquid is removed, and
Lignocellulose biomass is entered in pressurized reactor with about 45% dry matter.
Such as in the second experimental group, in initial trial, the lignocellulosic close to plug screw-feeder exit is raw
The density of substance plug is significantly less than the high densification sample that the lignocellulose biomass impregnated by compression individually produces
Density.Therefore, the portion of air in lignocellulose biomass is fallen into, but is not all of, can be fed by plug spiral
Device removal.
In pressurized reactor, by be used in the identical program that is described in detail in the first and second experimental groups be inserted into saturated vapor come
Pre-process the lignocellulose biomass impregnated.After the pre-treatment step of pressurized reactor, lignocellulose biomass is logical
It crosses gas blow pipe steam blasting and is recycled in the air blowing cyclone separator of about 0.5 bar pressure.
The control of three kinds of experimental groups and relative program
Different experiments group operates continuously in different operations, and runing time is up to 3 days.It is (every in initial start brief period
A experimental group is different) after, reach stable state.
First experimental group cannot work long hours, due to blocking up in the pressurized part between the first and second pressurized reactors
Lignocellulose biomass is filled in, is often stopped after operating a few houres.Second and third experimental group there is no it is any blocking ask
Topic.
According to well known formula, is calculated using the temperature of the steam head space measured under stable condition and residence time
Two and third experimental group process seriousness factor R 0:Log (R0)=Log [t*exp [T-100/14.75]],
Wherein t is the residence time as unit of minute, and T is the temperature of steam head space.
In the case where the first experimental group, it is contemplated that corresponding residence time and temperature in the first pressurized reactor, sternly
The principal characteristic factor further includes the first pre-treatment step.As being previously discussed in detail, the serious sex factor of the process is lignocellulosic
The level-one estimation of the serious sex factor of biomass experience.
Different processes is assessed according to xylan recycling and glucan accessibility.
Xylan recycling is the total amount and wood fibre of the xylose equivalent in pretreated lignocellulose biomass
The percentage of the cellulosic biomass amount of xylose equivalent existing for specified reference point in the process.Therefore, to the recycling of 100% xylose
Complementation represent as preprocessing process effect xylan degrading be degradation products total amount.
The composition of lignocellulose biomass and pretreated lignocellulose biomass, with regard to water content, glucose, wood
It is basis for sugar, cellobiose, xylobiose, wood oligose, glucose oligomer, insoluble glucan and insoluble xylan
NREL method NREL/TP 510 42618, NREL/TP 510 42623, NREL/TP 510 42621, NREL/TP 510
42620 measurements.All streams of different experiments group generation are considered in mass balance.In view of corresponding molecular weight, by institute
There is the sugar different from monomeric wood sugar to be converted into xylose equivalent.In all three experimental groups, reference point is entering whole process
It carries out immediately before, i.e., xylan, which recycles, is calculated relative to the lignocellulose biomass for entering process.
When the reference enzyme hydrolysis of time is fixed under fixed excessive enzyme, the accessibility of glucan is defined as solubility
Total amount of glucan at the end of reference enzyme hydrolysis (therefore including monomer and soluble oligomer) and pretreated wood fibre
The percentage of glucan total amount in cellulosic biomass.It, will by all sugar different from monomeric glucose in view of corresponding molecular weight
It is converted into glucose equivalents.
The accessibility representative of glucan can be with solvable shape in the hydrolytic process of pretreated lignocellulose biomass
The largest percentage of the glucan of formula recycling.
The accessibility of glucan is determined according to following programs.
Material previously treated and water with the volume mixture of 1500ml to obtain the mixture with 7.5% dry matter content, and
And mixture is inserted into enzyme reactor.PH value is set as 5.2 and temperature is set as 50 DEG C.Enzyme cocktail is added
(CTec3EU of Novozymes), corresponding concentration are to have 12 grams of mixture solution in the every 100 grams of solids for including in mixture.It is stirring
Mix lower progress enzyme hydrolysis in 48 hours.The content of glucan, glucose and glucose oligomer passes through standard HPLC points in mixture
Analysis is to measure.
Table 2 show the corresponding seriousness of operating parameter under stable state and the operation of three experimental group example process because
Son, and with regard to xylan recycling and glucan accessibility for whole process performance.
Relative to the first pre-treatment step/soaking step of experimental group, it is also reported that dividing from lignocellulose biomass
From the xylan dissolved in liquid flow percentage.It should be noted that second and the soaking step of third experimental group do not separate wood
Glycan, but in the first experimental group, some xylans are separated from lignocellulose biomass, this depends on the first pretreatment step
Rapid seriousness.
Relative to the second pre-treatment step/unique pre-treatment step of experimental group, it is also reported that if in steam head space
There is only pure steams will measure pressure.Δ P (Delta P) indicates the case where relative to pure steam in the aerial survety of steam top
Additonal pressure.In the operation twice of first experimental group (the second pre-treatment step), the pressure of measurement and the pure steaming at a temperature of measurement
Steam pressure is corresponding, therefore there is only steam in the steam head space of the second pressurized reactor of the first experimental group.
The first operation of first experimental group (wherein the first pre-treatment step carries out at temperature more higher than the second operation)
Show 87% high xylan recycling.Higher xylan amount is extracted in the first pre-treatment step, and in advance due to second
The lower temperature of processing step, a small amount of remaining xylan is dropped in the second pre-treatment step in lignocellulose biomass
Solution.Unfortunately, due to this low temperature, the accessibility of glucan only 83%, because second demands a lower price the low-steam pressure in reactor
Power is invalid in steam blasting.High temperature in second pre-treatment step increases the accessibility of glucan, but due to it is this compared with
The bigger amount of remaining xylan degrading under high-temperature, whole xylans, which recycles, to be reduced.
Second operation (wherein the first pre-treatment step carries out at a relatively low temperature) of the first experimental group is shown
64% low xylan recycling.Due to there is no to remove the xylan of correlative, corresponding to the steaming under the steam headspace pressure of measurement
Stripping temperature is degraded in the second pre-treatment step that they are carried out at high temperature.Glucan accessibility shows effective for 88%
Steam blasting.
In second and third experimental group, the steam headspace pressure of measurement is significantly beyond at a temperature of the steam head space of measurement
Pure steam pressure, show the air fallen into and to make gross pressure present in steam head space the lignocellulosic of additional contribution
Biomass is concomitantly introduced into pressurized reactor.It should be noted that corresponding to the bigger aeration in latter situation, in the second experimental group
Additonal pressure is about 2 bars and in third experimental group more than 6 bars.Air capacity present in steam head space can pass through dalton
The law of partial pressure calculates.However, equally in the case where the second experimental group, not by xylan from lignocellulose biomass
In the case where separation, 71% xylan recycling and 87% high beta-dextran accessibility can be obtained.Xylan recycling is by the
The limitation of the high temperature of two 206 DEG C of pre-treatment steps, this needs to reach 19 bars of pressure.It, can be in the case where third experimental group
The second pre-treatment step is operated in a low temperature of 196 DEG C, due to falling into air to the significant contribution of gross pressure in reactor, this is led
Cause very high 87% xylan recycling and 85% high beta-dextran accessibility.
Experiment shows that in second and third experimental group, the temperature and pressure in reactor is separated with balance of steam condition,
And it can be (according to avoid the need for significant xylan degrading) in low temperature and (according to the needs for reaching high beta-dextran accessibility)
Operate under high pressure, without in pressurizing vessel two step/two reactors of preextraction hemicellulose it is pretreated multiple
Polygamy and cost.
The procedure parameter and result of the example process operation of 2. 3 kinds of experimental groups of table
Claims (11)
1. a kind of method from lignocellulose biomass production biological product, the lignocellulose biomass includes total amount
Xylan, the glucan of total amount, total amount lignin and water, the method comprise the steps that
A. lignocellulose biomass, the gas of total amount and steam are introduced into the pressurized reactor of compressive reaction device assembly, institute
It states compressive reaction device assembly to operate in a continuous manner under conditions of pressurized reactor has steam head space, wherein a part is steamed
Vapour condenses on lignocellulose biomass and pressurized reactor；
B. so that lignocellulose biomass in pressurized reactor is maintained at the lignocellulose biomass pressure greater than 10 bars, stop
Time is 0.5 minute to 120 minutes, and steam head space temperature is within the scope of 130 DEG C to 230 DEG C, wherein lignocellulose biomass
Pressure ratio pure steam balance pressure at a temperature of steam head space is at least 1 bar big；
C. quick release lignocellulosic biomass while by the way that lignocellulose biomass is discharged from compressive reaction device assembly
Matter pressure refines lignocellulose biomass to generate pretreated lignocellulose biomass；
D. at least part glucan is hydrolyzed into a certain amount of glucose；
E. biological product is converted by the glucose of at least part amount.
2. the method according to claim 1, wherein the lignocellulose biomass further comprises the air fallen into, and extremely
Few a part of gas is to introduce the air fallen into described in pressurized reactor as described lignocellulose biomass a part.
3. method according to claim 1 or 2, wherein the method further includes xylan separating steps, wherein introducing
Before pressurized reactor, the xylan less than total amount 15% is separated from lignocellulose biomass.
4. method according to claim 1 or 2, wherein the method does not include xylan before introducing pressurized reactor
Separating step.
5. method according to claim 1 to 4, wherein the method further includes soaking steps, wherein
Before lignocellulose biomass is introduced pressurized reactor, lignocellulose biomass is immersed in the liquid including water and includes
In the liquid of water.
6. method according to claim 5, wherein the method further includes aerating steps, wherein after soaking step,
Lignocellulose biomass is aerated and lignocellulose biomass is exposed to air.
7. method according to any one of claim 1 to 6, wherein lignocellulose biomass is introduced compressive reaction
Before device, lignocellulose biomass is compressed within the scope of 25 DEG C to less than 100 DEG C of compression temperature.
8. method according to any one of claim 1 to 7, wherein pressurized reactor has pressurized reactor volume, and
And steam head space has steam head space volume, between the 5% to 80% of pressurized reactor volume.
9. method according to any one of claim 1 to 8, wherein selecting lignocellulose biomass pressure to refine
Step carries out steam blasting to lignocellulose biomass.
10. method according to any one of claim 1 to 9, wherein control steam head space temperature and residence time so as to
Recycle the xylan in pretreated lignocellulose biomass more than total amount 65%.
11. method according to any one of claim 1 to 10, wherein control lignocellulose biomass pressure, so that
Pretreated lignocellulose biomass includes a certain amount of accessible glucan, and pretreated lignocellulose biomass
In can contact glucan amount relative to glucan in pretreated lignocellulose biomass total amount be greater than 80%.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP16425038.3 | 2016-05-03 | ||
| EP16425038.3A EP3241907B1 (en) | 2016-05-03 | 2016-05-03 | Process for producing a bio-product |
| PCT/EP2017/060336 WO2017191091A1 (en) | 2016-05-03 | 2017-05-02 | Process for producing a bio-product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109072269A true CN109072269A (en) | 2018-12-21 |
| CN109072269B CN109072269B (en) | 2022-02-11 |
Family
ID=56121009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780025661.1A Active CN109072269B (en) | 2016-05-03 | 2017-05-02 | Method for producing biological products |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US11174498B2 (en) |
| EP (1) | EP3241907B1 (en) |
| CN (1) | CN109072269B (en) |
| BR (1) | BR112018071665A2 (en) |
| DK (1) | DK3241907T3 (en) |
| ES (1) | ES2717825T3 (en) |
| HR (1) | HRP20190560T1 (en) |
| HU (1) | HUE042465T2 (en) |
| LT (1) | LT3241907T (en) |
| PL (1) | PL3241907T3 (en) |
| PT (1) | PT3241907T (en) |
| RS (1) | RS58648B1 (en) |
| SI (1) | SI3241907T1 (en) |
| WO (1) | WO2017191091A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI128936B (en) * | 2020-03-11 | 2021-03-31 | Luonnonvarakeskus | Recovery of high-value components from biomass |
| CN115341004A (en) * | 2021-05-12 | 2022-11-15 | 国投生物科技投资有限公司 | Method for preparing monosaccharide from biomass raw material |
| IT202100031070A1 (en) | 2021-12-10 | 2023-06-10 | Versalis Spa | PROCEDURE FOR THE HYDRATION OF YEASTS IN DRIED FORM. |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102177293A (en) * | 2008-02-28 | 2011-09-07 | 安德里兹有限公司 | System and method for preextraction of hemicellulose through using a continuous prehydrolysis and steam explosion pretreatment process |
| CN102388144A (en) * | 2009-03-31 | 2012-03-21 | 康泰斯意大利有限公司 | Improved biomass pretreatment process |
| CN105492615A (en) * | 2012-08-01 | 2016-04-13 | 因比肯公司 | Methods of processing lignocellulosic biomass using single-stage autohydrolysis pretreatment and enzymatic hydrolysis |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2516833A (en) | 1947-06-09 | 1950-08-01 | Ant-Wuorinen Olli Viljo Anton | Process for hydrolyzing cellulosic materials |
| US4136207A (en) | 1977-01-24 | 1979-01-23 | Stake Technology Ltd. | Method of treating lignocellulose materials to produce ruminant feed |
| ES8201627A1 (en) * | 1980-02-23 | 1981-12-16 | Reitter Franz Johann | Process and apparatus for continuous hydrolysis of cellulosic plant materials for obtaining sugars. |
| CA2400336C (en) | 2000-02-17 | 2010-04-27 | Forskningscenter Riso | A method for processing lignocellulosic material |
| US7666637B2 (en) | 2006-09-05 | 2010-02-23 | Xuan Nghinh Nguyen | Integrated process for separation of lignocellulosic components to fermentable sugars for production of ethanol and chemicals |
| WO2013063478A1 (en) | 2011-10-28 | 2013-05-02 | Treefree Biomass Solutions, Inc. | Bioconversion of biomass to ethanol |
| RU2015114575A (en) | 2012-09-19 | 2016-11-10 | Андритц Инк. | METHOD AND APPARATUS FOR ADDING STEAM FOR THE STEAM EXPLOSION PROCESSING PROCESS |
| EP2765178A1 (en) | 2013-02-07 | 2014-08-13 | Arbaflame Technology AS | Method of producing carbon-enriched biomass material |
| ITTO20130711A1 (en) | 2013-09-02 | 2015-03-03 | Biochemtex Spa | COMPOSITIONS OF BIODERIVATED ETHYLENE GLYCOL FOR POLYESTER BOTTLES |
| CN104212531A (en) | 2014-09-25 | 2014-12-17 | 江南大学 | Method for preparing solid fuel by exploding biomass waste through external gas assisted by steam |
| MX360733B (en) | 2014-10-29 | 2018-11-14 | Cambi Tech As | Method and device for treating biomass and organic waste. |
-
2016
- 2016-05-03 RS RS20190396A patent/RS58648B1/en unknown
- 2016-05-03 HU HUE16425038A patent/HUE042465T2/en unknown
- 2016-05-03 EP EP16425038.3A patent/EP3241907B1/en active Active
- 2016-05-03 PT PT16425038T patent/PT3241907T/en unknown
- 2016-05-03 ES ES16425038T patent/ES2717825T3/en active Active
- 2016-05-03 LT LTEP16425038.3T patent/LT3241907T/en unknown
- 2016-05-03 DK DK16425038.3T patent/DK3241907T3/en active
- 2016-05-03 PL PL16425038T patent/PL3241907T3/en unknown
- 2016-05-03 SI SI201630217T patent/SI3241907T1/en unknown
-
2017
- 2017-05-02 CN CN201780025661.1A patent/CN109072269B/en active Active
- 2017-05-02 WO PCT/EP2017/060336 patent/WO2017191091A1/en active Application Filing
- 2017-05-02 US US16/095,996 patent/US11174498B2/en active Active
- 2017-05-02 BR BR112018071665-0A patent/BR112018071665A2/en unknown
-
2019
- 2019-03-22 HR HRP20190560TT patent/HRP20190560T1/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102177293A (en) * | 2008-02-28 | 2011-09-07 | 安德里兹有限公司 | System and method for preextraction of hemicellulose through using a continuous prehydrolysis and steam explosion pretreatment process |
| CN102388144A (en) * | 2009-03-31 | 2012-03-21 | 康泰斯意大利有限公司 | Improved biomass pretreatment process |
| CN105492615A (en) * | 2012-08-01 | 2016-04-13 | 因比肯公司 | Methods of processing lignocellulosic biomass using single-stage autohydrolysis pretreatment and enzymatic hydrolysis |
Non-Patent Citations (1)
| Title |
|---|
| FU XIAOGUO等: "Air–steam explosion enhancing the extraction efficiency of chlorogenic acid from leaves of Eucommia ulmoides Oliver", 《SEPARATION AND PURIFICATION TECHNOLOGY》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3241907A1 (en) | 2017-11-08 |
| EP3241907B1 (en) | 2018-12-26 |
| HRP20190560T1 (en) | 2019-05-03 |
| PL3241907T3 (en) | 2019-07-31 |
| US11174498B2 (en) | 2021-11-16 |
| CN109072269B (en) | 2022-02-11 |
| RS58648B1 (en) | 2019-05-31 |
| BR112018071665A2 (en) | 2019-02-19 |
| LT3241907T (en) | 2019-05-27 |
| ES2717825T3 (en) | 2019-06-25 |
| PT3241907T (en) | 2019-04-15 |
| US20190136279A1 (en) | 2019-05-09 |
| DK3241907T3 (en) | 2019-04-15 |
| HUE042465T2 (en) | 2019-07-29 |
| SI3241907T1 (en) | 2019-05-31 |
| WO2017191091A1 (en) | 2017-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2755981C (en) | Method for producing ethanol and co-products from cellulosic biomass | |
| Ewanick et al. | The effect of biomass moisture content on bioethanol yields from steam pretreated switchgrass and sugarcane bagasse | |
| US11236403B2 (en) | Method for treating lignocellulosic biomass by impregnation and steam explosion | |
| US9574212B2 (en) | Process comprising sulfur dioxide and/or sulfurous acid pretreatment and enzymatic hydrolysis | |
| US10179971B2 (en) | Method for processing a cellulosic feedstock at high consistency | |
| CN111788255B (en) | Method for treating lignocellulosic biomass by impregnation | |
| von Schenck et al. | Ethanol from Nordic wood raw material by simplified alkaline soda cooking pre-treatment | |
| US20110281298A1 (en) | Method and apparatus to extracted and reduce dissolved hemi-cellulosic solids in biomass following pre-hydrolysis | |
| CN109072269A (en) | The method for producing biological product | |
| KR20130140694A (en) | Pre-treated biomass having enhanced enzyme accessibility | |
| JP2021508355A (en) | How to treat lignocellulosic biomass | |
| Gu et al. | Fermentative high-titer ethanol production from douglas-fir forest residue without detoxification using SPORL: high SO2 loading at low temperature | |
| WO2013063478A1 (en) | Bioconversion of biomass to ethanol | |
| US20240026388A1 (en) | Method for treating a lignocellulosic biomass | |
| CN111770952B (en) | Method for treating lignocellulosic biomass | |
| Um | Evaluation of Secondary Acid and Enzymatic Hydrolysis of Hemicellulose in Hot Water Pre-Pulping Extract of Mixed Hardwoods | |
| US20120329116A1 (en) | Pretreatment of lignocellulosic biomass through removal of inhibitory compounds | |
| Souto-Maior | George JM Rocha, Vinícius FN Silva, Carlos Martín, Adilson R. Gonçalves, Viviane Marcos Nascimento & Ana |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220112 Address after: No. 1, poldrini Plaza, San Donato Milan, Italy Applicant after: Visalis AG Address before: Tortona, Italy 15057, 11, Ribrocastrada Applicant before: Beta Renewables S.P.A. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |